Ammonium and amine salts of di-perfluoroalkyl group containing acids and compositions and use thereof

ABSTRACT

Ammonium and amine salts of acids having the formula ##STR1## wherein R f  is a perfluoroalkyl group; R 1  is alkylene or substituted alkylene; X is --S--, --SO--, or --SO 2  --; R 2  is hydrogen, alkyl, aryl, substituted aryl, --B--COOH or a --B--COO anion; B is a covalent bond, arylene or alkylene; Z is the ammonium or amine cation; p is the anionic charge, q is the cationic charge; and p 1  and q 1  are the balanced mole equivalents respectively, are provided. These salts applied in the form of aqueous dispersions or emulsions, are useful in rendering cellulosic and natural and synthetic polyamide materials oil and water repellent.

This application is a continuation of now abandoned application Ser. No.515,755, filed July 21, 1983, which application is in turn a division ofapplication Ser. No. 292,326, filed Aug. 12, 1981 (now U.S. Pat. No.4,419,298).

BACKGROUND OF THE INVENTION

The instant invention is directed to salts of di-perfluoroalkyl groupcontaining acids with ammonia or amines, and the manufacture and use ofsuch salts in the form of aqueous emulsions or dispersions in treatingcellulosic materials and natural polyamide materials to render the sameoil and water repellent.

Di-perfluoroalkyl group containing acids, useful as starting materialsin the manufacture of the instant ammonium and amine salts, are, inpart, disclosed in U.S. Pat. No. 4,239,915, the disclosure of which isincorporated by reference herein. The di-perfluoroalkyl group containingacids are disclosed therein as useful inter alia for textile treating oras chromium complexes which possess oil and water repellent propertiesand are indicated as useful as grease or oil repellents for paper.Unfortunately, these acids possess, in general, very limited watersolubility and therefore require an organic solvent, or the like, forthe application of the di-perfluoroalkyl group containing acids to thecellulose, synthetic or natrual polyamide substrate in order to obtainthe desired oil and water repellent properties. Such organic solventcontaining solutions of the di-perfluoroalkyl group containing acidstend to be expensive due to the cost of such organic solvents. Moreover,the use of such organic solvent containing systems is often undesirabledue to odor, toxicity and flammability hazards. Furthermore, suchorganic solvent containing systems tend to be inefficient since much ofthe fluorochemical tends to remain in the organic solvent system duringthe application process and must be subsequently recovered from thespent organic solvent liquor for re-use. Also environmental problems areusually inherent in the use of organic solvent systems on an industrialscale.

It is an object of the present invention to avoid such problems byproviding to the artisan ammonium and amine salts of di-perfluoroalkylgroup containing acids. The ammonium and amine salts of the presentinvention are conveniently prepared by reacting the correspondingdi-perfluoroalkyl group containing acids with ammonia or the amine in adiluent substantially inert to the acid and ammonia or amine reactants,and recovering the amine salt formed. As the reaction between theammonia or amine and the acid takes place spontaneously, the reactioncan be conducted at temperatures between 0° C. and 100° C., preferablyat ambient temperature conditions. Where the amine is introduced ingaseous form, such as anhydrous ammonia or methyl amine, it can bebubbled through the acid in the liquid diluent medium. As the reactiontends to be exothermic, cooling of the reaction vessel may beadvantageously employed. Where the inert diluent is organic in nature,such as a lower alkanol, for example methanol, isopropanol, or the like,the ammonium or amine salt reaction product can be recovered byprecipitation, or evaporation of the diluent. If the inert diluent iswater, the ammonium or amine salt need not be separated from the aqueousmedia.

Where the amine is a quaternary ammonium compound, the resulting saltmay be obtained by adding together in the inert diluent, such as water,the di-perfluoroalkyl group containing acid with the quaternary ammoniumcompound in the base, or hydroxide form. Alternatively, thedi-perfluoroalkyl group containing acid may be neturalized with alkalior alkaline earth metal base, and the metal salt reacted with thequaternary ammonium compound in the halide form in an inert diluent bydouble displacement and the inorganic salt optionally separatedtherefrom by known extraction or precipitation techniques.

It is a further object of the invention to provide to the artisanaqueous emulsuions and dispersions of the ammonium and amine salts whichavoid the application problems associated with organic solventcontaining systems.

It is a further object of the present invention to provide the artisanwith efficient fluorochemical dispersions and emulsions providing highfluorochemical pick-up properties on cellulosic and natural polyamidesubstrates.

It is a further object of the present invention to provide the artisanwith fluorochemical treated cellulosic and natural polyamide containingmaterials possessing a high degree of oil and water repellentproperties, and a method of making the same.

These and other objects of the invention are apparent from the foregoingdisclosure.

DETAILED DISCLOSURE

One aspect of the instant invention relates to ammonium and amine saltsof gem-perfluoroalkyl group containing acids of the formula ##STR2##wherein

R_(f) is perfluoroalkyl of 4 to 18 carbon atoms orperfluoroalkoxy-perfluoroalkyl of 4 to 18 carbon atoms;

R₁ is straight or branched chain alkylene of 1 to 12 carbon atoms,alkylenethioalkylene of 2 to 12 carbon atoms, alkyleneoxyalkylene of 2to 12 carbon atoms, or alkyleneiminoalkylene of 2 to 12 carbon atomswhere the imino nitrogen atom contains as a third substituent, hydrogenor alkyl of 1 to 6 carbon atoms;

X is --S--, --SO-- or --SO₂ --;

R₂ is hydrogen, straight or branched chain alkyl of 1 to 6 carbon atoms,phenyl, alkyl substituted phenyl of up to 18 carbon atoms, or is thecarboxylic acid group --B--COOH, or

the carboxylate anion --B--COO;

B is a covalent bond, or alkylene of up to 18 carbon atoms, phenylene,phenoxyalkylene of 7 to 14 carbon atoms, phenylalkylene of 7 to 14carbon atoms, phenylalkylene of 7 to 14 carbon atoms, phenyalkenylene of8 to 14 carbon atoms, pr phenylene substituted by alkyl of 1 to 4 carbonatoms;

Z is the ammonium or amine cation;

p is the anionic charge of the gem-perfluoroalkyl group containing acidand is 1 or 2;

q is the cationic charge of the ammonium or amine group, Z, and has avalue of 1 to 200; and

The cationic mole equivalent, p₁ is equal to p and the anion moleequivalent, q₁, is equal to q, with the proviso that where p is 2 and qis an even integer, then p₁ is 1 and q₁ is g/2.

Preferably R_(f) is perfluoroalkyl of 6 to 14 carbon atoms, R₁ isstraight or branched chain alkylene of 2 to 8 carbon atoms, X is --S--or --SO₂ --, R₂ is hydrogen or alkyl of 1 to 4 carbon atoms, --B-- is acovalent bond or alkylene of 1 to 6 carbon atoms, p is 1 and q is 1 to4. In a more preferred embodiment, X is --S-- and q is 1 or 2.

Most preferably R_(f) is perfluoroalkyl of 6 to 12 carbon atoms, R₁ isalkylene of 2 to 4 carbon atoms, X is --S-- or --SO₂ --, R₂ is hydrogenor alkyl of 1 to 2 carbon atoms, --B-- is a covalent bond or alkylene of1 to 3 carbon atoms, p is 1 and q is 1 or 2.

Z is preferably the cation of ammonia, or of a water soluble mono- orpolyamine. Most preferably, Z is the cation of a water soluble mono- orpolyamine having a water solubility at 25° C. of at least 2% by weightin water.

Preferably, the amine cation is a cation of such a water soluble aminehaving the formula ##STR3## wherein

R₃ is hydrogen, alkyl of 1 to 5 carbon atoms; alkyl of 2 to 6 carbonatoms substituted by 2 to 6 hydroxy groups; alkenyl of 3 to 5 carbonatoms; cycloalkyl of 5 to 7 carbon atoms; -C₁ -C₃ -alkylene-COOH;##STR4## where m is 0 to 6, n is 0 to 30, and R₇ is hydrogen, alkyl of 1to 3 carbon atoms or alkanoyl of 2 to 4 carbon atoms; or is ##STR5##wherein s is 2 to 6, R₈ is hydrogen or alkyl of 1 to 3 carbon atoms, tis 0 or 1 and m, n and R₇ are as above defined; or is ##STR6## where R₉is straight or branched chain alkylene of 2 to 8 carbon atoms,cyclohexylene or di(C₁ to C₃ -alkylene)cyclohexylene, w is 0 to 198, R₁₀is hydrogen, alkyl of 1 to 3 carbon atoms, alkyl of 2 to 6 carbon atomssubstituted by hydroxy, or C₁ -C₃ -alkylene-COOH, and R₈ and t aredefined above; or is ##STR7## where a is 1 to 20, b is 2 to 50, c is 2to 20 and R₈ and t are as defined above;

R₄ and R₅ are independently hydrogen, alkyl of 1 to 5 carbon atoms or##STR8## where m, n and R₇ are as defined above; or R₄ and R₅ takentogether with the nitrogen to which they are attached representmorpholino; and

R₆ is alkyl of 1 to 5 carbon atoms; hydrogen when at least one of R₃, R₄and R₅ is other than hydrogen; alkyl of 6 to 23 carbon atoms when R₃ isother than hydrogen or alkyl of 1 to 5 carbon atoms; ##STR9## where m, nand R₇ are as defined above; or R₄, R₅ and R₆, taken together with thenitrogen which they are attached represent pyridyl; with the provisothat the total value of t equals q-1.

In a more preferred embodiment, R₃ is of the formula (CH₂ CH₂ --O)_(n) Hwhere n is 1 to 10, R₄ and R₅ are hydrogen or (CH₂ CH₂ --O)_(n) H wheren is 1 to 10 and R₆ is hydrogen, or (CH₂ CH₂ --O)_(n) H where n is 1 to10. Most preferably, n is 1 in each case.

Another more preferred embodiment, R₃ is of the formula (CH₂ CH₂--O)_(n) H where n is 1 to 10, R₄ is (CH₂ CH₂ --O)_(n) H where n is 1 to10, R₅ is hydrogen or (CH₂ CH₂ --O)_(n) H where n is 1 to 10 and R₆ isalkyl of 6 l to 20 carbon atoms. Most preferably, in this embodiment,the total value of n should be greater than 3 in order to insure thedesired solubility of the amine.

Advantageously, the solubility of the amine in water is determined onthe basis of free amine in water, or in the case of quaternary ammoniumcompounds, as the quaternary chloride.

In preparing the instant amine salts from polyamines, one may utilizeone or more equivalents of gem-perfluoroalkyl group containing acid permole of polyamine. Thus, where Z in formula I is a polyamine, one ormore amine nitrogens may be protonated, corresponding to the cationiccharge, q. In the preferred embodiment of the amine cation in formulaII, therefore, each additional protonated amine nitrogen, other than thenitrogen directly bonded to R₃, R₄, R₅ and R₆, is represented by thepresence of an R₈ group, i.e. where t equals 1 as to such aminenitrogen. Accordingly, the total number of protonated amine nitrogens isq, and the value of t equals q-1. Similarly, the value of p,corresponding to the anionic charge in formula I, is 2 when R₂ is thecarboxylate anion --B--COO, and is 1 where R₂ is other than --B--COO.

The cation mole equivalent in formula (I), p₁, is equal to the charge ofits counter ion, i.e. the anionic charge p, and the anion moleequivalent q₁ is equal to the charge of its counter ion, the cationiccharge q; except where p is 2 and q is an even integer, then p₁ is 1 andq₁ is g/2. Thus, for example, where the anion charge p is 2 and thecationic charge q is 3, then the balanced formula (I) contains 2equivalents of Z, or p₁ is 2, and 3 equivalents of the acid anion, or q₁is 3. Of course, where both the cation, Z, and the acid anion are bothdivalent, i.e. p and q are each 2, then there is one mole equivalent ofacid anion per mole equivalent of cation, or p₁ is 1, and q₁ is 2/2 or1.

Examples of highly advantageous amine cations include ##STR10## where Ris coco fatty alkyl and x+y is about 15, ##STR11## where R is steary andx+y is about 15, ##STR12## where R is tallow and x+y+z is about 10,##STR13## where a+c is 2 to 30 and b is 5 to 40, ##STR14## where R iscoco fatty alkyl and x+y+z is about 10, ##STR15##

Suitable amines which can be reacted with the gem-perfluoroalkylcontaining acids to form useful salts include aminomethane, aminoethane,1-aminopropane, 2-aminopropane, 1-aminobutane, 1-amino-2-methylpropane,1,1-dimethylethylamine, 1-aminopentane, isoamylamine, tert-amylamine,allylamine, dimethylamine, diethylamine, diisopropylamine,trimethylamine, triethylamine, tri-n-butylamine, ethylenediamine,1,2-propanediamine, trimethylenediamine, 1,3-diaminobutane,1,4-diaminobutane, hexamethylene diamine, diethylenetriamine,triethylenetriamine, tetraethylene pentamine, polyethyleneimine havingan average of about 20, 80, 120 or 200 units, diethylaminopropylamine,ethanolamine, diethanolamine, triethanolamine, ethylenediamine,tetraacetic acid, nitrilotrisacetic acid,N-(hydroxyethyl)ethylenenediamine,N,N"-bis-(hydroxyethyl)diethylenetriamine,N,N,N',N'-tetrakis-(2-hydroxypropyl)ethylenediamineN-(2-hydroxypropyl)-ethylene-diamine, cyclohexylamine,dicyclohexylamine, 1,8-diamino-p-menthane, and ##STR16## where R istallow fatty alkyl and x+y+z is 3, 10 or 15.

Suitable perfluoroalkyl acids useful in preparing the instant saltsinclude;

(C₈ F₁₇ CH₂ CH₂ S)₂ C(CH₃)CH₂ CH₂ COOH,

(C₆ F₁₃ CH₂ CH₂ S)₂ C(CH₃)CH₂ CH₂ COOH,

(C₈ F₁₇ CH₂ CH₂ S)₂ C(CH₃)COOH,

(C₆ F₁₃ CH₂ CH₂ S)₂ C(CH₂ CH₂ COOH)₂,

[(CF₃)₂ CFOCF₂ CF₂ CH₂ CH₂ S]₂ C(CH₂ CH₃)COOH,

(C₈ F₁₇ CH₂ CH₂ OCH₂ CH₂ CH₂ S)₂ C(CH₃)CH₂ COOH,

(C₈ F₁₇ CH₂ CH₂ N(CH₃)CH₂ CH₂ S)₂ C(CH₃)CH₂ COOH,

(C₈ F₁₇ CH₂ CH₂ SO₂)₂ C(CH₃)COOH, ##STR17## (C₈ F₁₇ CH₂ CH₂ S)₂CHC(CH₃)₂ CH₂ CH₂ COOH, and

(C₈ F₁₇ CH₂ CH₂ S)₂ CHCOOH.

The perfluoroalkyl acids useful in preparing the instant salts offormula I, where B is a covalent bond or alkylene can be prepared in themanner disclosed in U.S. Pat. No. 4,239,915. Those perfluoroalkyl acidsusedful in preparing the instant salts of formula I where B isphenylene, phenoxyalkylene of 7 to 14 carbon atoms, phenylalkenylene of8 to 14 carbon atoms or phenylene substituted by alkyl of 1 to 4 carbonatoms are prepared in an analogous manner. Thus, two moles of mercaptan,R_(f) --R₁ --SH is reacted per mole of either an aromatic aldehyde orketone of the formula R₂ --CO--B--COOH, optionally in the presence of acatalyst, such as hydrogen chloride or zinc chloride, or thecorresponding acetal or ketal in the presence of boron trifluorideetherate. The reaction is easily carried out in an inert solvent such asan aliphatic or aromatic hydrocarbon, which may be chlorinated orfluorinated, or in the absence thereof. Suitable solvents includeheptane, benzene, methylene chloride,1,1,2-trifluoro-1,2,2-trichloroethylene, chlorobenzene and the like.Also ethers, such as ethylene glycol dimethyl ether or tetrahydrofuranmay be used. The reaction mixture is advantageously kept at atemperature between room temperature and 80° C. under nitrogen until thereaction is completed. If desired, the resulting mercaptal, (R_(f) --R₁--S)₂ C(R₂)B--COOH, can be oxidized to the corresponding gem-sulfoxideand further, to the corresponding gem-sulfone by oxidation with thesuitable oxidizing agent, such as nitric acid, peracetic acid, potassiummonopersulfate, m-chloroperbenzoic acid and the like.

The gem-perfluoroalkyl group containing carboxylic acid amine salts areformulated as aqueous emulsion concentrates containing 5% to 40% byweight of the amine salt.

The aqueous emulsion concentrate is diluted to an application strengthsuch that the emulsion contains 0.01% to 2% by weight, more preferablybetween 0.05% and 0.30% by weight of the amine salt, based on the weightof cellulosic or natural or synthetic polyamide substrate.

Suitable cellulosic and natural polyamide substrates for topicalapplication include paper, non-woven fabrics, textiles, paperboard,wood, wood fiber products such as plywood, hair, including wool, hides,leather, and feathers. Synthetic polyamide substrates include nylonfibers and textiles.

For topical application, suitable aqueous emulsions contain,advantageously, 0.01% to 5%, preferably 0.02% to 2%, by weight of theamine salts at use dilution based on the weight of aqueous emulsion.Conventional adjuvants such as water repellant assistants,bacteriostats, coloring agents, surface conditioners and the like, maybe included, e.g in an amount of between about 0.01% and 5% by weight inthe emulsion. Also, sizing agents, where the emulsion is to be used oncellulosic substrates, may be present in amounts of from 0.01% to 10% byweight.

The sizing agent may be a natural sizing agent such as animal glue,asphalt emulsions, wax emulsions, rosins, starches; a semisyntheticsizing agent such as a fatty acid salt or complex, a fortified rosin.,e.g., tri sodium maleopimaric acid salt, sodium alginate or sodiumcarboxymethylcellulose; or a synthetic sizing agent such as analkylketene dimer, alkylsuccinic anhydrides, polyvinyl alcohol,styrene-maleic anhydride polymers, and the like. Also mixtures thereofmay be used.

Asphalt emulsions include those obtained from natural deposits or fromthe residue of crude petroleum distillation and emulsified in an aqueoussolution with an emulsifier such as sodium rosinate or fatty amine. Waxemulsions include those prepared from paraffin waxes, optionally blendedwith rosin size and emulsified with a suitable emulsifier, such as guargum, gum arabic, stearic acid salts, lignosulfonate salts, alkylaminesalts, and the like. Starches include corn starch, potato starch, wheatstarch, ethylated corn starch, cationic corn starch corn starch acetate,and the like. Fatty acid salts and complexes include, for example,stearic acid salts, e.g., of aluminum and zirconium, and thecorresponding myristic acid, lauric acid, palmitic acid, margaric acidand behenic acid salts and the corresponding chromium complexes of theseacids with chromium salts, including the Werner type complexes of afatty acid, such as stearic or myristic acid with chromium chloride andisopropanol.

Alkylketene dimers include those wherein the alkyl group is between 6 to23 carbon atoms such as the palmitic, stearic, oleic and myristic ketenedimers, as well as those where the alkyl group is unsaturated orbranched chain, and mixtures thereof.

Alkylsuccinic anhydrides include those where the alkyl group is straightor branched chain and may be saturated or unsaturated having betweenabout 6 to 23 carbon atoms, such as the n-hexadecenylsuccinic anhydride,the dodecylsuccinic anhydride, the dodecenylsuccinic anhydride, theisooctadecenylsuccinic anhydride, and the like.

Also alkylcarbamoyl chlorides, such as ditallowamine carbamoyl chloride;gelatins, cationic aqueous polyurethane emulsions, acrylic resins,stearyl amine surfactants, as known in the art, are suitable sizingagents.

Fillers include materials such as kaolin clay, calcium carbonate, alum,magnesium sulfate, sodium chloride, and the like.

Bacteriostats and fungicides are those commonly used in the paper,leather, fur and textile industries and include halogenated phenols,halogenated carbanilides, o-phenylphenol, salicylic acid anilide,2,2'-methylene-bis(4-chlorophenol), tetraaliphatic ammonium bromides orchlorides, hydroxyquinoline and the like.

Coloring agents include titanium dioxide, and other conventionalinorganic pigments, organic pigments, dyes and optical brighteners.

Surface conditioner adjuvants include paper sizing lubricants, such as afatty acid/polyethylene glycol stearate mixture; swelling agents, suchas an amine oxide swelling agent; extenders, such as urea; fillerretention aids, such as colloidal silica and methyl cellulose; and thelike.

Also, as discussed below, an emulsifier may also be optionally presentin an amount of between about 0.001% to 3% by weight in the emulsion.

Thus, suitable aqueous emulsions for topical application contain--

(a) 0.01 to 5% by weight of the amine salt;

(b) 0 to 3% by weight emulsifier;

(c) 0 to 5% water repellant assistant, filler, bacteriostat, coloringagent or surface conditioner adjuvant;

(d) 0 to 10% sizing agent, and

(e) the remainder water.

These emulsions are applied to the surface of the cellulosic or naturalor synthetic polyamide material by conventional techniques, includingpadding, spraying, coating, washing, and brushing. After application,the treated surface is dried, with or without an intermediate washingstage. The resulting surface is thus rendered water and oil resistant.

For use as an internal sizing agent to obtain oil and water repellency,the dilution of the instant aqueous emulsions advantageously containfrom about 0.0005 to 0.2% by weight of the instant amine salts. Theemulsions for dilution may be prepared as a concentrate containingbetween 5% and 40% by weight, preferably 15 to 25% by weight, of theamine salt, based on the amount of water.

In order to insure emulsion stability of the amine salt in the aqueousmedium, the emulsion is advantageously prepared in the presence of aconventional emulsifier. Suitable emulsifiers include cationic, anionic,amphoteric and non-ionic emulsifiers. It is preferred to use non-ionicemulsifiers, such as block copolymers of ethylene oxide and propyleneoxide.

The amount of emulsifier used, will, of course depend upon theemulsification characteristics of the amine salt chosen, as well as thedesired concentration of the amine salt in the aqueous medium. Whereconcentrated emulsions are desired, having between 10 and 40% by weightof the amine salt, it is convenient to use up to 5% of emulsifier. Inmany cases, little or no emulsifier need be added to obtain a stable,aqueous emulsion.

Preferably, when present, the emulsifier is present in the emulsionconcentrate in an amount between 0.01 and about 3% by weight.

Suitable emulsifiers for use in the present invention includeconventional cationic emulsifiers which are compatible with the activeamine salts of the di-perfluoroalkyl group acids, and conventionalnonionic emulsifiers.

Preferred emulsifiers are non-ionic emulsifers including ethoxylatedlong chain aliphatic amines, ethoxylated long chain aliphatic esters,ethers and thioethers, ethoxylated alkylphenols, block copolymers ofethylene oxide and propylene oxide, and block copolymers of ethyleneoxide and propylene oxide on an alkylene polyamine.

Most preferred nonionic emulsifiers are ethylene oxide/propylene oxideblock copolymers, polyethoxylated octyl and nonyl phenols, and blockcopolymers of ethylene oxide and propylene oxide on ethylene diamine.Suitable nonionic emulsifers are widely commercially available, such asPluronics, including Pluronic F-68, F-87 and F-98 from BASF WyandotteCorp., Tritons, including Triton X-35 and X-114 from Rohm and HaasCorp.; Igepals; including Igepal CO-710 and CO-730 from GAF Corp.; andTetronics, such as Tetronic 904, from BASF Wyandotte Corp.

Pluronics are prepared by condensing ethylene oxide with a hydrophobicbase formed by the condensation of propylene oxide with propylene glycoland may be represented empirically by the formula:

    HO--(C.sub.2 H.sub.4 O).sub.a (C.sub.3 H.sub.6 O).sub.b (C.sub.2 H.sub.4 O).sub.c H.

Pluronic F-68 contains about 80% ethylene oxide units (C₂ H₄ O) and themolecular weight of the polypropylene oxide block (C₃ H₆ O)_(b) is about1,750. Pluronic F-87 contains about 70% ethylene oxide units (C₂ H₄ O)and the molecular weight of the polypropylene oxide block (C₃ H₆ O)_(b)is about 2,250. Pluronic F-98 contains about 80% ethylene oxide units(C₂ H₄ O) and the molecular weight of the polypropylene oxide block (C₃H₆ O)_(b) is about 2,750.

Triton nonionic alkylphenol surfactants are ethoxylated t-octylphenolsor ethoxylated nonylphenols. Triton X-35 is an ethoxylated octylphenolhaving 3 ethylene oxide units and Triton X-114 is likewise anethoxylated octylphenol having 7 to 8 ethylene oxide units, IgepalCO-710 is an ethoxylated nonylphenol having 71% combined ethylene oxideunits by weight of nonylphenol and Igepal CO-730 is an ethoxylatednonylphenol having 73% combined ethylene oxide units by weight ofnonylphenol.

Tetronic 904 is an ethylenediamine/propylene oxide ethylene oxide adductof the approximate formula ##STR18##

While the instant aqueous emulsions are suitable for rendering a varietyof cellulosic and natural and synthetic polyamide materials oil andwater repellant, the instant emulsions are particularly advantageous inrendering articles made from paper pulp, such as paper trays, paperplates and analogous paper articles, both oleophobic and hydrophobic.

In order to further increase the efficiency of application of theemulsion to the paper pulp, it is desirable to pre-treat the paper pulpwith a cationic agent, such as cationically modified starch, which isadsorbed by the paper pulp and, consequently, tends to increase theamount of fluorochemical transferred from the aqueous emulsion to thecellulose substrate.

Suitable cationic agents, conventionally used to pretreat cellulosematerials such as paper pulp, include conventional cationic modifiedstarches, such as Interbond C, Lok-Size 30, Cato 2, Cato 15 and Cato 17;cationic modified aminoplast resins such as Kymene 557 from HerculesInc.; cationic polymers such as Santo-Res 21 from Monsanto or Reten-210from Hercules Inc.; and cationic blocked polyurethanes such as HypolWB-4000 from W. R. Grace Inc.

Cationic starches are prepared by reacting the starch with amines orquaternary ammonium compounds. Thus, amino ethers of starch are producedby reacting starch with a dialkylaminoalkyl halide which has the aminogroup in the beta-position, as disclosed, for example, in U.S. Pat. No.2,970,140 and Canadian Pat. No. 699,812, both of which describe usefulcationic starches. Further useful cationic starches are described inU.S. Pat. Nos. 2,876,217 and 3,346,563.

Jointly with the gem-perfluoroalkyl group containing acid salts of theinvention, can be added one or more of wide choice of water proofingsizing agents selected from classes such as alkyl anhydrides, e.g.Fibron 68; alkyl ketene dimers e.g. Aquapel 360 XC or Hercon 40;polyurethane emulsions, e.g. Graphsize C; acrylic resins, e.g. Carboset;stearyl amine surfactants, e.g., Ethomeen 18/25 complexed with a fattyacid, e.g. stearic acid; Neofat 14, Neofat 47 or Hystrene 9718.

The amount of adjuvant and sizing agent used for treating paper pulp isof the range specified for topical application, supra.

Thus, for internal sizing of paper pulp suitable aqueous emulsionscontain

(a) 0.0005 to 0.1% by weight of the instant amine salts;

(b) 0.00001 to 0.05% by weight emulsifier;

(c) 0 to 5% by weight filler, bacteriostat, fungicide, coloring agent orsurface conditioner adjuvant;

(d) 0 to 10% sizing agent; and

(e) the remainder water.

The following examples are intended for illustrative purposes only, andare not intended to restrict the scope of the invention in any way. Allparts are by weight unless otherwise specified.

EXAMPLES

The following paragraphs describe the preparation of a number ofammonium and amine salts of gem-bis-perfluoroalkyl acids and theirusefulness in imparting oil and water repellency to a variety ofsubstrates.

The preparation of many of these useful fluorinated acids is describedin U.S. Pat. No. 4,239,915 (R. A. Falk; assigned to Ciba-GeigyCorporation).

A number of other related acids can also be prepared such as:

4,4-Dimethyl-5,5-bis(1,1,2,2,-tetrahydro perfluorodecylthio)-pentanoicacid ##STR19##

1,1,2,2-tetrahydroperfluoroalkyldecane-thiol (192 g, 0.4 mole),4-methyl-4-formylo-pentanoic acid (28.8 g, 0.2 mole), and 100 g oftoluene were added to a 500 ml Erlenmeyer flask equipped with a magneticstirring bar. Anhydrous hydrogen chloride was bubbled through thesolution for 2 hours and the reaction mixture was then stirredovernight. The white precipitate which formed was collected and washedwith methanol/water (1:1), filtered and dried (183 g, 84% yield, m.p.83°-85° C.).

Analysis for C₂₇ H₂₀ F₃₄ O₂ S₂ : calc.: C 29.83%, H 1.84%, F 59.48%.found: C 29.93%, H 1.67%, F 58.91%.

¹ H-NMR spectrum: 1.08 ppm(s), 1.87 ppm(m), 2.05-3.15(m), 3.52 ppm(s),10.8(s) in a ratio of approx. 6:2:10:1:1.

4-Carboxy-benzaldehyde-bis-(1,1,2,2-tetrahydroperfluorodecylthio)-acetal##STR20##

1,1,2,2-tetrahydroperfluorodecane-thiol (48 g, 0.1 mole),4-carboxy-benzaldehyde (7.5 g, 0.05 mole) and 120 g of toluene wereadded to a 500 ml Erlenmeyer flask equipped with a magnetic stirringbar. Anhydrous hydrogen chloride was bubbled through the solution for 2hours. The white precipitate which resulted was collected by filtration,washed with methanol/water (1:1), filtered again, and dried. (54 g, 99%yield, m.p. 134°-136° C.).

Analysis for C₂₈ H₁₄ F₃₄ O₂ S₂ : calc.: C 30.77%, H 1.28%, F 59.16%.found: C 30.90%, H 1.33%, F 58.33%.

¹ H-NMR spectrum: 2.85 ppm (m), 5.88 ppm (s), 7.80 (m), 8.14 ppm (m),10.30 ppm (s) in a ratio of approx. 8:1:2:2:1.

In a similar manner, the following compound can be prepared fromo-formylphenoxyacetic acid: ##STR21##

The corresponding sulfoxides and sulfones can be prepared from thesegem-bis-perfluoroalkyl-thio acids in the usual way with conventionaloxidizing agents such as: hydrogen peroxide, peracetic acid, potassiummonopersulfate, m-chloroperbenzoic acid, and the like.

The following examples also describe the preparation of many ammoniumand amine salts of a number of these gem-bis-perfluoroalkyl carboxylicacids by conventional means. Additionally, the ammonium and amine saltsof this invention can also be prepared by the reaction of ammoniumhydroxides or quaternary alkyl ammonium hydroxides with the fluorinatedacids. These are shown in examples 1 and 14.

Another alternative method of preparation, is the reaction of the alkalimetal salts of the fluorinated acids with quaternary ammonium halides orhydrohalides. Such as the following:

(a) (R_(f) CH₂ CH₂ S)₂ CHCOO.sup.⊖ Na.sup.⊕ +R₃ N.sup.⊕.Cl.sup.⊖ (R_(f)CH₂ CH₂ S)₂ CHCOO.sup.⊖.N.sup.⊕ R₃ +NaCl

(b) (R_(f) CH₂ CH₂ S)₂ CHCOO.sup.⊖ Na.sup.⊕ +R₂ N.sup.⊕ H Cl.sup.⊖→(R_(f) CH₂ CH₂ S)₂ CHCOO.sup.⊖ HN.sup.⊕ R₂ +NaCl

The by-product salts (e.g., NaCl) could be removed by appropriateion-exchange resins or dialysis membranes.

The examples that follow illustrate a number of the compounds which areincluded in this invention and their utility. The compounds of thisinvention are not necessarily limited to those exemplified.

                                      TABLE I                                     __________________________________________________________________________    Examples                                                                      Gem-perfluoroalkylthio Group Containing Acids                                 Designation                                                                   for subsequent                      R.sub.f -distribution (%)                 examples                                                                              Structure                   C.sub.6 F.sub.13                                                                   C.sub.8 F.sub.17                                                                    C.sub.10 F.sub.21                                                                  C.sub.12 F.sub.25                                                                   C.sub.14                                                                      F.sub.29            __________________________________________________________________________    A.sub.1 (R.sub.f CH.sub.2 CH.sub.2 S).sub.2 C(CH.sub.3)CH.sub.2 CH.sub.2              COOH                        6    36    46   11    1                   A.sub.2 (R.sub.f CH.sub.2 CH.sub.2 S).sub.2 C(CH.sub.3)CH.sub.2 CH.sub.2              COOH                        2     7    71   11    1                   A.sub.3 (R.sub.f CH.sub.2 CH.sub.2 S).sub.2 C(CH.sub.3)CH.sub.2 CH.sub.2              COOH                        6    30    49   13    2                   B       (R.sub.f CH.sub.2 CH.sub.2 S).sub.2 CHCOOH                                                                13   84     3   --    --                  C       (R.sub.f CH.sub.2 CH.sub.2 S).sub.2 C(COOH)CH.sub.2 CH.sub.2                                              7OOH 35    46   11    1                   D       [(CH.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 CH.sub.2 CH.sub.2 S].sub.2             C(CH.sub.2 CH.sub.3)COOH                                              E       [(CH.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 CH.sub.2 CH.sub.2 S].sub.2             C(CH.sub.3)CH.sub.2 COOH                                              F       *(C.sub.6 F.sub.13 CH.sub.2 CH.sub.2 S).sub.2 C(φ)CH.sub.2                CH.sub.2 COOH                                                         G       (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 S).sub.2                C(COOH).sub.2                                                         H       (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2               S).sub.2 C(CH.sub.3)CH.sub.2 COOH                                     I       [C.sub.8 F.sub.17 (CH.sub.2).sub.2 N(CH.sub.3)(CH.sub.2).sub.3                S]C(CH.sub.3)CH.sub.2 COOH                                            J       (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 S).sub.2 C(CH.sub.3)COOH          K       (C.sub.6 F.sub.13 CH.sub.2 CH.sub.2 S).sub.2 C(CH.sub.2 CH.sub.2              COOH).sub.2                                                           L       (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SO.sub.2).sub.2 C(CH.sub.3)CH.            sub.2 CH.sub.2 COOH                                                   M       (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 S).sub.2 CHC(CH.sub.3).sub.2              CH.sub.2 CH.sub.2 COOH                                                         ##STR22##                                                            O                                                                                      ##STR23##                                                            P       (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 S).sub.2 CHCOOH                   __________________________________________________________________________     *(φ = phenyl)                                                        

EXAMPLES 1-15

This group of examples illustrates a number of the amines and ammoniumcompounds which are useful for the preparation of the salts of thisinvention.

Ten gram portions of the fluorochemical acid A₁ in Table I were weighedinto 2 ounce glass jars with the amines listed in Table II, and 30.0 gof methylene chloride. Several stainless-steel balls were added to aidmixing.

The jars were capped, shaken, and placed on a rolling device overnight.The products were then collected by filtration and dried under vacuum atroom temperature.

EXAMPLES 16-29

These examples demonstrate how the above salts can be converted intouseful emulsions or dispersions.

The R_(f) -acid amine salts listed in the above examples (see Table II)were each placed in 2 ounce jars with distilled water, and Pluronic F-68(wetting aid, from BASF Wyandotte). These mixtures were then stirred at60°-65° C. for 20 minutes. Several stainless-steel balls were added andthe jars were placed on a rolling device overnight. These examples ofaqueous dispersions are listed in Table III.

                                      TABLE II                                    __________________________________________________________________________    Examples 1-15                                                                 Ex-                          grams of                                                                           approx. wgt. of  melting                    am-                          amine                                                                              mole ratio                                                                            dry salt range % Fluorine           ple                                                                              Amine                     used R.sub.f -acid: amine                                                                  collected                                                                          yield                                                                             of salt                                                                             calc.ree.C.)         __________________________________________________________________________    1  ammonium hydroxide        1.5  1:1     10.3 g                                                                             97.7%                                                                             106-108                                                                             61.0                    29.4% NH.sub.4 OH in water                                                 2  monoethanolamine          0.56 1:1     10.5 g                                                                             99.0                                                                              110-130                                                                             59.7                    H.sub.2 NCH.sub.2 CH.sub.2 OH                                              3  diethanolamine            1.0  1:1      9.9 g                                                                             89.6                                                                              104-131                                                                             57.7                    HN(CH.sub.2 CH.sub.2 OH).sub.2                                             4  triethanolamine           1.37 1:1     10.7 g                                                                             93.7                                                                              104-134                                                                             55.8                    N(CH.sub.2 CH.sub.2 OH).sub.3                                              5  Ethomeen C/25 (Armak)     8.16 1:1     11.3 g                                                                             62.3                                                                              86-90 36.1                     ##STR24##                                                                 6  Ethomeen 18/25 (Armak)    8.3  1:1     11.5 g                                                                             62.7                                                                              93-94 35.8                     ##STR25##                                                                 7  Ethoduomeen T-20 (Armak)  1.97   1:0.5  9.4 g                                                                             78.3                                                                               99-103                                                                             53.2                     ##STR26##                                                                 8  Jeffamine ED-900 (Jefferson)                                                                            4.5    1:0.5  8.9 g                                                                             61.1                                                                              83-85 44.6                     ##STR27##                                                                 9  Jeffamine ED-2001 (Jefferson)                                                                           10.8   1:0.5 16.5 g                                                                             79.1                                                                              90-96 31.6                    same as ED-900 except 88%                                                     ethylene oxide                                                             10 DMAMP - 80 (IMC)          1.34 1:1      9.3 g                                                                             82.1                                                                              87-91 57.2                    (CH.sub.3).sub. 2CCH.sub.2 OH 80% in water                                    N(CH.sub.3).sub.2                                                          11 AMP (IMC)                 0.41   1:0.5 10.3 g                                                                             99.3                                                                               99-115                                                                             60.6                     ##STR28##                                                                 12 tetrasodium EDTA          3.81 1:1     13.5 g                                                                             97.8                                                                              >220  51.1                     ##STR29##                                                                 13 tetrasodium EDTA          1.91   1:0.5 11.7 g                                                                             98.3                                                                              >220  52.7                    same as above                                                              14 tetramethylammonium hydroxide                                                                           4.17 1:1      8.9 g                                                                             63.0                                                                              159-164                                                                             60.5                    (CH.sub.3).sub.4 NOH (20% in methanol)                                     15 Quadrol (BASF-Wyandotte)  1.34   1:0.5  9.8 g                                                                             86.2                                                                               89-101                                                                             56.0                     ##STR30##                                                                 __________________________________________________________________________

                                      TABLE III                                   __________________________________________________________________________    Examples 16-29                                                                 ##STR31##                                                                                     weight of                                                                          weight of                                                                              calculated     pH of a                                          dist.                                                                              10% solution                                                                           solids                                                                              Appearance                                                                             1% dilution                     Example                                                                            made from   water                                                                              of Pluronic F-68                                                                       content                                                                             of dispersion                                                                          (w/v) in water                  __________________________________________________________________________    16   4.0 g example 1 salt                                                                      34.0 g                                                                             3.0 g    10.5% free flowing,                                                                          8.6                                  (ammonium hydroxide)            opalescent liquid                        17   4.0 g example 2 salt                                                                      16.5 g                                                                             3.0 g    18.3% free flowing,                                                                          10.0                                 (monoethanolamine)              translucent                              18   4.0 g example 3 salt                                                                      16.5 g                                                                             3.0 g    18.3% free flowing,                                                                          9.1                                  (diethanolamine)                translucent liquid                       19   4.0 g example 4 salt                                                                      22.9 g                                                                             3.0 g    14.4% free flowing,                                                                          7.2                                  (triethanolamine)               translucent liquid                       20   4.0 g example 5 salt                                                                      16.0 g                                                                             none     20.0% free flowing,                                                                          7.7                                  (Ethomeen c/25)                 milky white liquid                       21   4.0 g example 6 salt                                                                      16.0 g                                                                             none     20.0% free flowing,                                                                          9.0                                  (Ethomeen 18/25)                milky white liquid                       22   4.0 g example 7 salt                                                                      16.3 g                                                                             3.0 g    18.5% pale-yellow cream                                                                      6.5                                  (Ethoduomeen T-20)                                                       23   4.0 g example 8 salt                                                                      27.5 g                                                                             0.5 g    12.7% free flowing,                                                                          8.7                                  (Jeffamine ED-900)              opalescent liquid                        24   4.0 g example 9 salt                                                                      19.5 g                                                                             none     17.0% free flowing,                                                                          9.7                                  (Jeffamine ED-2001)             opalescent liquid                        25   4.0 g example 10 salt                                                                     40.0 g                                                                             3.0 g     9.2% fairly viscous                                                                         9.2                                  (DMAMP)                         opalescent liquid                        26   4.0 g example 11 salt                                                                     28.2 g                                                                             3.0 g    12.2% opaque viscous                                                                         9.5                                  (AMP)                           liquid                                   27   4.0 g example 12 salt                                                                     28.2 g                                                                             3.0 g    12.3% opalescent                                                                             9.5                                  (Na.sub.4 EDTA)                 viscous liquid                           28   4.0 g example 14 salt                                                                     16.5 g                                                                             3.0 g    18.3% fairly viscous                                                                         9.5                                  (tetramethyl ammonium           opalescent liquid                             hydroxide)                                                               29   4.0 g example 15 salt                                                                     16.4 g                                                                             3.0 g    18.4% fairly viscous                                                                         9.8                                  (Quadrol)                       opaque liquid                            __________________________________________________________________________

EXAMPLE 30

A 1.00 g sample of (R_(f) CH₂ CH₂ S)₂ CHCOO⁻⁺ N(CH₃)₄ was made into anaqueous dispersion, in the same manner as examples 16-29, with: 4.02 gdist. water, 0.10 g diethanolamine, and 0.75 g of a 10% solution ofPluronic F-68 (wetting aid).

R_(f) =6% C₆ F₁₃, 36% C₈ F₁₇, 46% C₁₀ F₂₅, 1% C₁₄ F₂₉.

EXAMPLE 31

By an alternative method, the salt and dispersion were formedsimultaneously, in one operation, by weighting 6.84 g dist. water, 0.17g diethanolamine, 1.20 g of 10% ag. Pluronic F-68, and 1.59 g acid B (inTable I) into a 2 ounce jar. The contents were stirred at 60° C. for 10min. The jar was capped and placed on a rotating device for severaldays. A viscous, slightly cloudy liquid resulted. At 1% in water, the pHwas 10.0.

EXAMPLES 32-37

Several dispersing and/or wetting aids were utilized in these exampleswhich are listed in Table IV. Two grams of acid A₂ from table I, 0.162 gdiethanolamine, and the amount and type of wetting aid shown in Table IVwere mixed with 2 grams of distilled water at 55° C.; then diluted withadditional water (see Table IV). After additional mixing at 55° C.; thedispersions, in 2 ounce jars, were rotated overnight.

EXAMPLE 38

In this example, the salt and dispersion were also prepared in oneoperation.

To a 20-liter glass reactor, equipped with a motor driven stirrer,thermometer, nitrogen inlet, and vent; were charged 1755 g dist. waterand 195 g Pluronic F-68 (powder). This was stirred at 35°-40° C. untildissolved. Then 273.3 diethanolamine (2.60 moles) and 8900 g dist. waterwere added with stirring. Then 3702 g of a paste containing 74% acid A₃from Table I in water and methanol (2.25 moles) were charged in followedby 174.4 g dist. water. The mixture was stirred at 60°-65° C. for 4hours. A viscous, light-straw colored, translucent liquid resulted.

solids: calculated=21.3%, found=21.5%. fluorine in solids:calculated=53.0%, found=53.50%.

The above dispersion formed a clear bluish solution when diluted to 1%(as is) in dist. water, pH=9.7.

                                      TABLE IV                                    __________________________________________________________________________    Examples 32-37                                                                 ##STR32##                                                                                                     additional                                                                          total                                  Dispersing/wetting aid           water batch                                                                             Appearance                         Example                                                                            amount* trade-name                                                                              type      added size                                                                              of dispersion                      __________________________________________________________________________    32       0.62 g                                                                            Tetronic 504                                                                            propylene oxide-                                                                         6.36 g                                                                             12.52 g                                                                           white paste                             mix     Tetronic 701                                                                            ethylene oxide                                                  1.38 g                                                                            (BASF-Wyandotte)                                                                        adducts of ethylene                                                           diamine                                                33       1.0 g                                                                             Triton X-35                                                                             octylphenoxy                                                                            12.64 g                                                                             17.8 g                                                                            white paste                                     (Rohm & Haas)                                                                           polyethoxyethanol                                      34       1.0 g                                                                             Triton X-114                                                                            octylphenoxy                                                                            12.64 g                                                                             17.8 g                                                                            somewhat viscous,                                         polyethoxyethanol   free-flowing, hazy                                                            liquid                             35       1.0 g                                                                             Pluronic F-68                                                                           ethylene oxide,                                                                         12.64 g                                                                             17.8 g                                                                            somewhat viscous,                               (BASF-Wyandotte)                                                                        proplylene oxide,   free-flowing, hazy                                        ethylene oxide      liquid                                                    block polymers                                         36       1.0 g                                                                             Pluronic F-87                                                                           ethylene oxide,                                                                         12.64 g                                                                             17.8 g                                                                            somewhat viscous,                                         propylene oxide,    free-flowing, hazy                                        ethylene oxide      liquid                                                    block polymers                                         37       1.0 g                                                                             Pluronic F-127                                                                          ethylene oxide,                                                                         12.64 g                                                                             17.8 g                                                                            somewhat viscous,                                         propylene oxide,    free-flowing, hazy                                        ethylene oxide      liquid                                                    block polymers                                         __________________________________________________________________________     *Weight of 10% (w/v) solutions in water.                                 

EXAMPLES 39-42

Aqueous dispersions of acid A₃ (listed in Table I) were made withseveral other amines. The preparation of the salts and dispersions werecarried out in one operation. These examples are listed in Table V.Distilled water, the amine, wetting aid, and fluorinated acid wereblended together in a 2 ounce jar, stirred for 10 min. at 60° C., andplaced on a rotating device overnight.

EXAMPLE 43

The use of another of the fluorinated acids is described in thisexample.

By the method described in Example 31, a dispersion was prepared from7.92 g dist. water, 0.34 g diethanolamine, 2.0 g of a 10% aq. PluronicF-98 solution, and 2.0 g of acid C in Table 1. An opalescent liquidresulted.

EXAMPLE 44-51

The use of a number of other fluorinated acids and amines is describedin this group of examples.

Using the methods and techniques described in examples 1-29, theexamples listed in Table VI are prepared.

                                      TABLE V                                     __________________________________________________________________________    Eamples 39-42                                                                                Wgt. of                                   pH of a              Wgt. of   Wgt. of                                                                            Pluronic                                                                           Amine               Dispersion       1% dilution          Example                                                                            R.sub.f -acid                                                                      water                                                                              F-68*                                                                              amount                                                                            type            calc. % solids                                                                       appearance                                                                              in                   __________________________________________________________________________                                                             water                39   4.0 g                                                                              15.96 g                                                                            3.0 g                                                                              0.54 g                                                                            triethanolamine 20.6   free-flowing,                                                                           10.0y                                                               white liquid                   40   4.0 g                                                                              16.18 g                                                                            3.0 g                                                                              0.32 g                                                                            AMP (IMC)       19.7   slightly                                                                                 9.5ous,                                     2-amino-2-methyl-1-propanol                                                                          opalescent liquid              41   4.0 g                                                                              15.50 g                                                                            3.0 g                                                                              1.00 g                                                                            Diam-G21 (Henkel)                                                                             22.6   viscous,                                                                                10.2my                                       N--coco-1,3-propane diamine                                                                          white liquid                   42   4.0 g                                                                              15.22 g                                                                            3.0 g                                                                              1.28 g                                                                            Ethomeen T-12 (Armak)                                                                         23.7   separated --                                           bis-(2-hydroxyethyl)-tallowamine                      __________________________________________________________________________     *As 10% (w/v) solution in water.                                         

                                      TABLE VI                                    __________________________________________________________________________    Examples 44-51                                                                     R.sub.f -acid                                                                 as listed                                                                Example                                                                            in Table I                                                                          Amine      Product                                                 __________________________________________________________________________    44   D     stearyl amine                                                                            [(CF.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 CH.sub.2                               CH.sub.2 S].sub.2 C(CH.sub.2 CH.sub.3)COO.sup..crclb                          ar..H.sub.3 N.sup.⊕C.sub.18 H.sub.37                45   E     diethylamine                                                                             [(CF.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 CH.sub.2                               CH.sub.2 S].sub.2 C(CH.sub.3)CH.sub.2 COC.sup.⊕.                          H.sub.2 N.sup.⊕ (CH.sub.2 CH.sub.3).sub.2           46   F     guanidine  [(C.sub.6 F.sub.13 CH.sub.2 CH.sub.2 S).sub.2                                 C(phenyl)CH.sub.2 CH.sub.2 COO.sup.⊖                                  ].sub.2.(H.sub.3 N.sup.⊕).sub.2 CNH                 47   G     triethylamine                                                                            (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 CH.sub.2                                  CH.sub.2 S).sub.2 C(COO.sup.⊖).sub.2.[HN.sup                          .⊕ (CH.sub.2 CH.sub.3).sub.3 ].sub.2                48   H     pyridine                                                                                  ##STR33##                                              49   I     melamine                                                                                  ##STR34##                                              50   J     poly(ethylenimine)                                                                       [(C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 S).sub.2                                 C(CH.sub.3)COO.sup.⊖ ] ˜.sub.180.sup..                          sym.NH.sub.3(CH.sub.2 CH.sub.2 N.sup.⊕ H.sub.                             2) ˜.sub.179 H                                    51   K     Duomeen C (Armak)                                                                         ##STR35##                                                                    where R = coco                                          __________________________________________________________________________

Example 52

This example describes the use of a bis-sulfone type of acid.

Using the method described in example 31, a dispersion was prepared from6.64 g dist. water, 2.20 g of 10% aq. Pluronic F-68, 0.21 gdiethanolamine, and 2.00 g of acid L (from Table I). A fluid translucentwhite liquid resulted (at 22.0% solids). A 1% dilution in water produceda hazy solution at pH 9.7.

The following examples illustrate how the compounds and dispersions ofthe previous examples can be used to impart oil and water repellentproperties to a variety of substrates.

APPLICATION EXAMPLES Example 53

Samples of fluorochemical dispersion of the type described in example 38were added to a 10% aqueous solution of paper maker's starch (pHadjusted to 9.6 with 10% aq. NaOH). This starch solution was applied tounsized paper by padding (paper dipped through starch solution, thenpassed through single nip rollers). The resulting sheets of paper weredried at ambient conditions for 15 minutes, then for 3 minutes at 200°F. in an "Emerson Speed Drier" (heated metal plate with canvas cover).Table VII lists the results.

                  TABLE VII                                                       ______________________________________                                        Example 53                                                                    amount of dry      amount of                                                  fluorochem                                                                              weight   fluorochem.                                                                              oil kit                                                                             Gurley-Cobb                               dispersion                                                                              pick-up  solids to  num-  test-water                                added.sub.1                                                                             of starch                                                                              wgt. of paper                                                                            ber.sup.2,3                                                                         absorbed.sup.2,4                          ______________________________________                                        a   none      5.8%     none     0     121. g/M.sup.2                          b   6 ml      5.2%     0.036%   5     12.8 g/M.sup.2                          c   8 ml      4.2%     0.039%   6     13.7 g/M.sup.2                          d   10 ml     5.1%     0.060%   6     12.6 g/M.sup.2                          ______________________________________                                         notes:                                                                        .sup.1 amount shown was prediluted 1:1 with dist. water and added into 10     ml starch solution at 150° F.                                          .sup.2 measured on side facing canvas in drier.                               .sup.3 OIL KIT for Surface Oil Resistance Tests (TAPPI method UM557)          .sup.4 Cobb size test, ASTM method D3285-73; measurements made after 15       second exposure to water.                                                

An easily made kit of twelve solutions of varying proportions of CastorOil, Toluene, and Heptane is useful in comparing surface oil resistance.

    ______________________________________                                        Kit                                                                           No.  Volume Castor Oil                                                                          Volume Toluene                                                                             Volume Heptane                                 ______________________________________                                        1    200           0            0                                             2    180          10           10                                             3    160          20           20                                             4    140          30           30                                             5    120          40           40                                             6    100          50           50                                             7     80          60           60                                             8     60          70           70                                             9     40          80           80                                             10    20          90           90                                             11    0           100          100                                            12    0           90           110                                            ______________________________________                                    

The "kit value" is defined as the highest number solution that willstand on the surface of the plate for 15 seconds in the form of dropswithout failing. Failure is detected by pronounced darkening caused bypenetration. The darkening of even a small fraction of the area underthe drop is considered failure.

Example 54

A 4% solution of cationic starch is distilled water was prepared bycooking in a double boiler. When cooled, 50 ml of this starch solutionwas placed into a beaker followed by 50 ml of a 2% as is (0.426% solids)solution of fluorochemical dispersion of the type described in example38. This mixture was then pad applied (as is example 53) to unsized,bleached, kraft paper at 100% wet pick-up. The resulting paper was dried(as in example 53) at 220° F. for 20 minutes. The treated paperdemonstrated an oil kit number (TAPPI UM-557) of 12 and a Gurley-Cobbsizing value of 24 gm/M² of water absorbed, compared to a kit number of0 and Cobb test of 183 g/M² with cationic starch alone with nofluorochemical.

Example 55

This example demonstrates the utility of these dispersions as internalsizes.

Six grams of dry bleached Kraft pulp were diluted in 289 ml distilledwater and thoroughly dispersed in a blender. To this pulp slurry wasadded 3.6 ml of a 1% dilution (as is) of the dispersion from example 31in distilled water. This was mixed in for 5 minutes, then 6 ml of a 1%aqueous solution of cooked cationic starch was added. This was mixedtogether for an additional 5 minutes. To this, 1.2 ml of a 1.5% (onsolids) dilution of an alkyl ketene dimer emulsion was added as a waterrepellent adjuvant. This was mixed in for another 10 minutes. Theresulting slurry was diluted with an additional 500 ml of dist. waterand mixed again. This mixture was then poured over a 100 mesh wirescreen, with a vacuum applied from below which pulled the water from thepulp mixture to form a sheet on the screen. The wet sheet was removedfrom the screen and dried between another screen and hard surface at apressure of approximately 0.4 lbs/in.² at 110° C. for 11/2 hours. Thepaper formed in this manner, showed a TAPPI method UM-557 oil kit numberof 4 (see example 53). One ml of hot (110° C.) corn oil placed on thepaper remained on the surface and did not penetrate for 12 minutes.Similarly, 1 ml of hot (80° C.) water containing 0.5% of Triton X-165wetting agent (from Rohm & Haas) placed on the paper did not penetratefor 20 minutes. Whereas, paper made in the same manner, including thecationic starch and water repellant adjuvant but without thefluorochemical dispersion; demonstrated an oil kit number of <1, andheld the hot corn oil and hot water/Triton X-165 solution for less thanone minute (began to penetrate as soon as applied).

Examples 56-58

Three pad bath solutions were made up, each containing: 8.6 ml of thesame kind of fluorochemical dispersion as described in example 38, 2.5ml of Aerotex M-3 textile resin (at 80% actives, from AmericanCyanamid), 0.4 ml Aerotex Accelerator UTX, 0.1 ml Mykon NRW-3 (wettingagent from Sun Chemical), and 88.4 ml distilled water.

These pad baths were then applied to the substrates shown in Table VIIIat a 50% wet pickup (one pass through bath into single nip rollers). Thetreated samples were dried at 110° C. for 2 minutes and cured at 163° C.for 3 minutes. Water and oil repellency measurements were then made. Theresults are shown in Table VIII. Application of the same system withoutthe fluorochemical dispersion resulted in no oil or water repellency(zero ratings).

                  TABLE VIII                                                      ______________________________________                                        Examples 56-58                                                                Ex-                 Oil Repellency                                                                            Water Repellency                              ample Substrate     Rating.sup.1                                                                              Rating.sup.2                                  ______________________________________                                        56    fiber reinforced                                                                            5           50                                                  cellulose based                                                               non-woven fabric                                                        57    100% filament 4           90                                                  Nylon poncho                                                            58    100% spun Dacron                                                                            4            80.sup.-                                     ______________________________________                                         .sup.1 Oil Repellency: AATCC test method no. 1181975                          .sup.2 Water Repellency: AATCC test method no. 221974                    

Examples 59-63

For purposes of comparison, mono-perfluoroalkyl chain containingcarboxylic acid compounds and a sample of a commercial fluorochemicalpaper size (3M's FC-807, twin-R_(f) -tailed phosphate ester, ammoniumsalt) were tested against the gem-bisperfluoroalkylthio group containingacids of this invention (Examples 59-62). The compounds were applied asaqueous dispersions or solutions and evaluated in a manner similar tothat described in example 55 (i.e. internal size). These tests are shownin table IX.

                                      TABLE IX                                    __________________________________________________________________________    Examples 59-63                                                                                                     alkyl       Hold-out tests*                                        fluorine                                                                           cationic                                                                            Ketene dimer                                                                         oil hot,                                                                           110° C.                                                                      hot, 80°                                                               C.                                               on wgt.                                                                            starch                                                                              adjuvant                                                                             Kit  corn  water + 0.5%           Example                                                                            Fluorochemical       of paper                                                                           in paper                                                                            in paper                                                                             number                                                                             oil   Triton                 __________________________________________________________________________                                                           X-165                  59   diethanolamine salt of                                                                             0.08%                                                                              1.0%  0.3%   5    >20 min.                                                                            20 min.                     (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 S).sub.2 C(CH.sub.3)CH.sub.2              CH.sub.2)COOH                                                                 aqueous dispersion prepared                                                   as in example 31                                                         60   diethanolamine salt of                                                                             "    "     "      1-2  <1 min.                                                                             <1 min.                     C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 COOH,                   aqueous solution                                                         61   diethanolamine salt of                                                                             "    "     "      2    2 min.                                                                              3 min.                      C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SCH.sub.2 COOH,                            aqueous solution                                                         62   aqueous dispersion of the                                                                          0.04%                                                                              "     0.3%   4    20 min.                                                                             20 min.                     same type as in example 38                                                                         "    "      0.45% 3-4  >20 min.                                                                            15-20 min.                  (diethanolamine salt of                                                                            0.06%                                                                              "     0.3%   5    >20 min.                                                                            20 min.                     acid A.sub.3 in table I)                                                                           "    "      0.45% 5    >20 min.                                                                            20 min.                63   Scotchban FC-807 (3M Co.)                                                                          0.04%                                                                              "     0.3%   2-3  <1 min.                                                                             15-20 min.                  bis-perfluoroalkyl phosphate                                                                       "    "      0.45% 3    <1 min.                                                                             15-20 min.                  ester, ammonium salt 0.06%                                                                              "     0.3%   5    >20 min.                                                                            20 min.                                               "      0.45% 4    >20 min.                                                                            >20                    __________________________________________________________________________                                                           min.                    *Hold-out tests observed for up to 20 minutes.                           

Example 64

In this example, the salt of the sulfone type acid (L) was evaluated asan internal paper size.

The fluorochemical dispersion of example 52 was applied and tested bythe method described in example 55. At an application level of 0.78%dispersion to weight of dry pulp; an oil kit value of 5 was obtained,the sheet held out the hot corn oil for more than 20 minutes, and heldout the hot water + Triton X-165 solution for about 20 minutes.

Example 65

In this example, the salt of another acid (M) was also evaluated as aninternal size.

By the method described in example 31, a dispersion was prepared from14.05 g dist. water, 3.00 g of 10% aq. Pluronic F-68, 0.43 gdiethanolamine, and 4.00 g of acid M (from Table I). This produced atranslucent white paste (22% solids). At 1% in water, the pH was 9.5.

This fluorochemical dispersion was then evaluated by the method ofexample 55. It showed the same performance as listed in example 64.

Example 66

By the method described in example 54, the dispersion from example 65(acid M) was evaluated as an external paper size. A mixture of 50 ml of4% cationic starch, 20 ml of the fluorochemical dispersion (diluted to5% as is), and 30 ml dist. water were pad applied to the paper. Thedried sheet showed an oil Kit number of 9, and a Gurley-Cobb sizingvalue of 57 g/M² (water absorbed).

Example 67

In this example, the dispersion of acid N (from Table I) was preparedand evaluated as an external paper size.

By the method described in example 31, an aqueous fluorochemicaldispersion was prepared from 14.03 g dist. water, 3.00 g of a 10%solution of Pluronic F-68, 0.42 g of diethanolamine, and 4.00 g of acidN (aromatic type). The resulting product was a milky white (almosttranslucent paste)--giving a pH of 9.28 at 1% in water.

This was applied and tested as above (example 66). The dried sheet ofpaper had an oil Kit number of 6 and a Gurley-Cobb sizing value of 80g/M².

Example 68

In this example, an aqueous dispersion was prepared from acid P (intable I) and also evaluated as an external size on paper.

By the method described in example 31; 14.16 g of dist. water, 3.00 g ofa 10% solution of Pluronic F-68, 0.46 g of diethanolamine, and 4.00 g ofacid P (with 61.87% F found) were combined to form a translucentlight-straw colored liquid which had a pH of 9.07 when diluted to 1% inwater.

When applied and tested as in example 66, the resulting treated paperhad an oil Kit value of 3 and a Cobb-size rating of 103 g/M² (waterabsorbed).

Example 69

In this example the acid of the formula ##STR36## was prepared by thefollowing procedure:

p-Formylcinnamic acid, 15.0 g (0.085 moles), n-C₈ F₁₇ CH₂ CH₂ SH, 82.5 g(0.17 moles) and acetic acid, 200.0 g, were charged to the reactionflask and the temperature was raised and held at 81° C. to dissolve thep-formylcinnamic acid. Hydrogen chloride gas was introduced for 10minutes during which time a white solid precipitated out of solution.The resulting solids were filtered, washed with aqueous methanol anddried in a 60° C. vacuum oven overnight. The yield was 95.9% of whitepowder.

    ______________________________________                                        Elemental analysis                                                                      % calculated                                                                           % found                                                    ______________________________________                                        C           32.21      32.34                                                  H            1.44       1.32                                                  F           57.75      56.83                                                  S            5.73       6.55                                                  ______________________________________                                    

Example 70

As in Example 68, an aqueous emulsion was prepared from 13.77 g dist.water, 4.40 g of a 10% solution of pluronic F-68, 0.56 g diethanolamine,and 4.00 g of acid ")", listed in Table I, and prepared in accordancewith Example 69. This produced a white liquid which had a pH of 9.3 at1% in water.

When applied and tested as above, the treated paper had an oil kitnumber of 8 and a Cobb-size value of 17 g/M² (water absorbed).

What is claimed is:
 1. An aqueous emulsion concentrate containing 5% to40% by weight of a compound of the formula ##STR37## wherein R_(f) isperfluoroalkyl of 6 to 14 carbon atoms;R₁ is straight or branched chainalkylene of 2 to 8 carbon atoms; X is --S-- or --SO₂ --; R₂ is hydrogenor alkyl of 1 to 4 carbon atoms; B is a covalent bond or alkylene of 1to 6 carbon atoms; and Z is the cation of mono-, di-, ortri-ethanolamine.
 2. An aqueous emulsion or dispersion for topicalapplication to a cellulosic or natural or synthetic polyamide substrate,to render the substrate oil and water repellant comprising(a) 0.01 to 5%by weight of the amine salt of the formula ##STR38## wherein R_(f) isperfluoroalkyl of 6 to 14 carbon atoms;R₁ is straight or branched chainalkylene of 2 to 8 carbon atoms; X is --S-- or --SO₂ --; R₂ is hydrogenor alkyl of 1 to 4 carbon atoms; B is a covalent bond or alkylene of 1to 6 carbon atoms; and Z is the cation of mono-, di-, ortri-ethanolamine (b) 0 to 3% by weight emulsifier; (c) 0 to 5% by weightfiller, water repellant assistant, bacteriostat, coloring agent orsurface conditioner adjuvant; (d) 0 to 10% by weight sizing agent, and(e) the remainder water.
 3. An aqueous emulsion or dispersion accordingto claim 2 containing 0.001 to 3% by weight of said emulsifier.
 4. Anaqueous emulsion or dispersion according to claim 3 wherein theemulsifier is a non-ionic emulsifier.
 5. An aqueous emulsion ordispersion according to claim 2 containing 0.01 to 5% by weight of saidsurface conditioner adjuvant.
 6. An aqueous emulsion or dispersion fortopical application to a cellulosic substrate, according to claim 2,containing 0.01 to 10% by weight of said sizing agent.
 7. An aqueousemulsion for the internal sizing of paper pulp, to render the same oiland water repellant, comprising(a) 0.0005 to 0.1% by weight of an aminesalt of the formula ##STR39## wherein R_(f) is perfluoroalkyl of 6 to 14carbon atoms;R₁ is straight or branched chain alkylene of 2 to 8 carbonatoms; X is --S-- or --SO_(2--;) R₂ is hydrogen or alkyl of 1 to 4carbon atoms; B is a covalent bond or alkylene of 1 to 6 carbon atoms;and Z is the cation of mono-, di-, or tri-ethanolamine (b) 0.00001 to0.05% by weight emulsifier; (c) 0 to 5% by weight filler, bacteriostat,fungicide, coloring agent or surface conditioner adjuvant; (d) 0 to 10%sizing agent; and (e) the remainder water.
 8. An aqueous emulsionaccording to claim 7, wherein the emulsifier is a nonionic emulsifier.9. A process for rendering a cellulosic or natural or syntheticpolyamide substrate oil and water repellant comprising the steps ofcontacting said substrate with an effective amount of an aqueousemulsion according to claim 2, and drying the treated substrate.
 10. Aprocess for the internal sizing of paper pulp, comprising contactingsaid paper pulp with an effective amount of an aqueous emulsionaccording to claim 6, to render the pulp oil and water repellant, andsubsequently drying the pulp.
 11. A process according to claim 9,wherein said paper pulp is pretreated with a cationic agent.
 12. Aprocess according to claim 11, wherein the cationic agent is acationically modified starch, a cationic modified aminoplast resin, acationic polymer or a cationic blocked polyurethane.
 13. A processaccording to claim 11, wherein the cationic agent is a cationicallymodified starch.
 14. A water and oil repellant cellulosic, or natural orsynthetic polyamide, substrate produced according to the process ofclaim
 9. 15. An oil and water repellant paper pulp article producedaccording to the process of claim
 10. 16. An oil and water repellantpaper pulp article produced according to the process of claim 12.